Issue 72, 2014

Base-free chemoselective transfer hydrogenation of nitroarenes to anilines with formic acid as hydrogen source by a reusable heterogeneous Pd/ZrP catalyst

Abstract

A highly efficient, chemoselective, environmentally-benign method is developed for the catalytic transfer hydrogenation (CTH) of nitroarenes using FA as a hydrogen source. Various supported Pd catalysts were examined for this transformation, and Pd supported ZrP (Pd/ZrP) proved to be the best catalyst for CTH of nitrobenzene. Applicability of the Pd/ZrP catalyst is also explored for hydrogenation of various substituted nitroarenes. The Pd/ZrP catalyst showed high specificity for hydrogenation of nitro groups even in the presence of other reducible functional groups such as –C[double bond, length as m-dash]C, –COOCH3, and –C[triple bond, length as m-dash]N. To investigate the reaction mechanism, a Hammett plot was obtained for CTH of p-substituted nitroarenes. The active site is thought to be in situ generated Pd(0) species as seen from XRD and TEM data. The Pd/ZrP catalyst is reusable at least up to 4 times while maintaining the same activity and selectivity. To the best of our knowledge, this is one of the best methodologies for CTH of nitroarenes under base-free conditions with high activity and chemoselectivity over heterogeneous Pd-based catalysts.

Graphical abstract: Base-free chemoselective transfer hydrogenation of nitroarenes to anilines with formic acid as hydrogen source by a reusable heterogeneous Pd/ZrP catalyst

Supplementary files

Article information

Article type
Paper
Submitted
24 Jun 2014
Accepted
08 Aug 2014
First published
11 Aug 2014

RSC Adv., 2014,4, 38241-38249

Base-free chemoselective transfer hydrogenation of nitroarenes to anilines with formic acid as hydrogen source by a reusable heterogeneous Pd/ZrP catalyst

J. Tuteja, S. Nishimura and K. Ebitani, RSC Adv., 2014, 4, 38241 DOI: 10.1039/C4RA06174H

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